CN107460462B - The preparation method of silver nano-grain compacted zone on silicon wafer - Google Patents
The preparation method of silver nano-grain compacted zone on silicon wafer Download PDFInfo
- Publication number
- CN107460462B CN107460462B CN201710707061.5A CN201710707061A CN107460462B CN 107460462 B CN107460462 B CN 107460462B CN 201710707061 A CN201710707061 A CN 201710707061A CN 107460462 B CN107460462 B CN 107460462B
- Authority
- CN
- China
- Prior art keywords
- silicon wafer
- solution
- preparation
- silver
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to the preparation method of silver nano-grain compacted zone on silicon wafer, steps are as follows: silicon wafer is first placed on to alkali wash water and pickling solution immersion makes silicon chip surface hydroxylating；Being placed in reaction in the toluene solution of mercaptopropyi trimethoxy silane makes silicon wafer silanization；It is successively respectively placed in silver nitrate solution and sodium borohydride solution to generate silver-colored seed crystal；It is placed in the mixed solution of silver nitrate and polyvinylpyrrolidone, instills ascorbic acid solution later so that silver-colored seed crystal is constantly grown up；It is rinsed after repeatedly, and ultrasound drying.Silver-colored seed crystal by means of being first fixed on silicon wafer by the present invention with difunctional organic molecule, in-situ reducing obtains silver-colored seed crystal later, pass through the multiple cycling deposition in later period again, fine and close, uniform Argent grain film layer can be obtained, this metallic particles film layer is in SERS application, (such as micron range) uniform, higher reinforcing effect can be kept in the larger context, and this preparation method is reproducible.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, and in particular to the system of silver nano-grain compacted zone on a kind of silicon wafer
Preparation Method.
Background technique
It is found in the research of Surface enhanced Raman spectroscopy (SERS), the base formed due to nano-metal particle close-packed arrays
Enhancing of the bottom to light field, will lead to the enhancing of Raman signal intensity.When between particle be in Nano grade gap when, particle it
Between electric field be mutually coupled, enhanced intensity is more significant, and Raman signal is caused significantly to be promoted.Therefore for SERS substrate,
The research hotspot that high Raman reinforcing effect is the industry is obtained in order to keep the distance between particle small as far as possible.
The method for preparing SERS substrate usually has etching method and colloidal solid solwution method:
Wherein etching method needs special equipment and many and diverse preparation section, and is difficult in Nano grade control
Intergranular away from.When the distance between Argent grain is between 100nm or so (Proc. Of SPIE Vol.8323 83232L), particle
Field coupling can almost ignore, therefore very high reinforcing effect can not be obtained in SERS application, therefore this method is only
It is limited to theoretic explanation, there is no actual applications.
Colloidal solid solwution method (Small 2014,10, No.3,609-616) is molten by the colloid in silver nano-grain
NaCl is added to reduce the distance between Ag particle in liquid, and deposition obtains intensive Ag particle on silicon wafer.This method preparation
In nanoparticle agglomerates body, although the gap between particle is in Nano grade, acquired Argent grain distribution is not uniform enough,
And most particulate interspaces are still very big, are unfavorable for obtaining uniform, effective reinforcing effect in SERS application, and prepare knot
The poor repeatability of fruit, therefore SERE result cannot be not only consistent in the detection of different batches, it is different even if same substrate
Also gap is larger for test result at position, cannot function as a kind of stable SERS substrate.
In addition, preparation SERS can also pre-process silicon chip with substrate, pass through in-situ reducing, self-assembled nanometer metal
Particle is on silicon wafer.It mentions, silicon wafer is modified using amino silane, then in patent of invention (CN201510753537.X)
It places it in silver nitrate and ammonia spirit, the SERS substrate of modified by silver nanoparticles silicon face is obtained by in-situ reducing.
The picture provided from it is as it can be seen that the silver nano-grain distribution of silicon chip surface is sparse, and distribution is also extremely uneven, and partial particulate is serious
Reunite, therefore high, uniform SERS reinforcing effect cannot be obtained, is only capable of detecting concentration being 10-8Luo Danming-the B of mol/L points
The Raman spectrum of son.It is mentioned in patent of invention (CN201510973724.9) and the silicon wafer after aminosilane-treated is placed in gold chloride
In solution, by the week reduction of amino in silicon chip surface in-situ preparation nanogold particle, but distribution of the particle on silicon wafer
Still extremely sparse, enhancement factor is only 10 when causing to detect glycerol molecule4The order of magnitude.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of silver nano-grain compacted zone on silicon wafer, with obtain it is fine and close,
Uniform Argent grain film layer makes it in SERS application, uniform, higher enhancing can be kept to imitate in the larger context
Fruit, and it is reproducible.
The technical scheme adopted by the invention is as follows:
The preparation method of silver nano-grain compacted zone on silicon wafer, it is characterised in that:
The following steps are included:
Silicon wafer: being first placed on alkali wash water by step 1 and pickling solution impregnates each 15 minutes, so that silicon chip surface hydroxylating；
Step 2: the silicon wafer that step 1 is obtained is placed in the toluene solution of mercaptopropyi trimethoxy silane, 40 DEG C of temperature
Degree lower reaction 4-10 hours, or react 24-40 hours at room temperature, so that silicon wafer silanization；
Step 3: the silicon wafer that step 2 is obtained, which is placed in the silver nitrate solution of 0.25mM, to be impregnated 6-24 hours；
Step 4: the silicon wafer that step 3 obtains is taken out, is placed in the sodium borohydride solution of 5mM, is reacted 30 minutes；
Step 5: the silicon wafer that step 4 obtains is taken out, is placed in the mixed solution of silver nitrate and polyvinylpyrrolidone, stirs
It mixes 30 minutes, instills the ascorbic acid solution of 1ml, 0.5mM later；
Step 6: the silicon wafer that step 5 obtains is taken out, is rinsed with deionized water, is repeated step 5 2-5 times；
Step 7: finally taking out reacted silicon wafer and rinsed with a large amount of deionized waters, and 2 points of ultrasound in deionized water
Clock, drying.
In step 1, alkali wash water is mixed to get by ammonium hydroxide, hydrogen peroxide, water, volume ratio 1:1:5.
In step 1, pickling solution is mixed to get by hydrochloric acid, hydrogen peroxide, water, volume ratio 1:1:5.
It in step 1, is rinsed, and is cleaned by ultrasonic 2 minutes with a large amount of deionized waters after alkali cleaning and pickling.
In step 1, the silicon wafer of surface hydroxylation is with being dried with nitrogen.
In step 2, in the toluene solution of mercaptopropyi trimethoxy silane, the volume of mercaptopropyi trimethoxy silane
Concentration 1-5%.
In step 2, the silicon wafer of silanization is respectively placed in toluene, the toluene/ethanol mixed liquor of ethyl alcohol volume ratio 1:1, second
Each ultrasonic 2 minutes in alcohol, deionized water.
In step 3, the silicon wafer after immersion is rinsed with deionized water, ultrasound 2 minutes.
In step 4, the silicon wafer after reaction is rinsed with deionized water, ultrasound 2 minutes.
In step 5, in the mixed solution of silver nitrate and polyvinylpyrrolidone, the concentration of silver nitrate is 0.25mM, poly- second
The concentration of alkene pyrrolidone is 0.75mM.
The invention has the following advantages that
Preparation method proposed by the present invention, by means of silver-colored seed crystal is first fixed on silicon wafer with difunctional organic molecule
On, then by the multiple cycling deposition in later period, fine and close, uniform Argent grain film layer can be obtained, this metallic particles film layer exists
In SERS application, (such as micron range) uniform, higher reinforcing effect can be kept in the larger context, and this is prepared
Method is reproducible.
The substrate prepared by this method, is shown in Fig. 1, Argent grain on a silicon substrate densely, be evenly distributed, between particle
Average distance be less than 10nm, this substrate can detect 10-11R6G solution when mol/L concentration.And on this base not
With the measurement result (see figure 2) at position, closely, relative standard deviation (RSD) is 4%, illustrates the uniformity of substrate very
It is good.
Particle arrangement is fine and close, i.e., particulate interspaces are small, are most important for obtaining high enhancement factor in SERS is applied
, for this substrate since silver nano-grain is uniformly distributed, it is also uniform that the SERS of molecular detection, which is enhanced, will not be because of spy
Survey molecule in substrate the difference of distributing position and there is the Raman diffused light spectral intensity of varying strength, hereby it is ensured that SERS survey
The confidence level and uniformity of test result.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture for the Argent grain being grown on silicon wafer.
Fig. 2 is the raman scattering spectrum of the R6G solution of multiple random positions in substrate.
Specific embodiment
The present invention will be described in detail With reference to embodiment.
The preparation method of silver nano-grain compacted zone on silicon wafer of the present invention, comprising the following steps:
Silicon wafer: being first placed on alkali wash water by step 1 and pickling solution impregnates each 15 minutes, so that silicon chip surface hydroxylating；
Step 2: the silicon wafer that step 1 is obtained is placed in the toluene solution of mercaptopropyi trimethoxy silane, 40 DEG C of temperature
Degree lower reaction 4-10 hours, or react 24-40 hours at room temperature, so that silicon wafer silanization；
Step 3: the silicon wafer that step 2 is obtained, which is placed in the silver nitrate solution of 0.25mM, to be impregnated 6-24 hours；
Step 4: the silicon wafer that step 3 obtains is taken out, is placed in the sodium borohydride solution of 5mM, is reacted 30 minutes；
Step 5: the silicon wafer that step 4 obtains is taken out, is placed in the mixed solution of silver nitrate and polyvinylpyrrolidone, stirs
It mixes 30 minutes, instills the ascorbic acid solution of 1ml, 0.5mM later；
Step 6: the silicon wafer that step 5 obtains is taken out, is rinsed with deionized water, is repeated step 5 2-5 times；
Step 7: finally taking out reacted silicon wafer and rinsed with a large amount of deionized waters, and 2 points of ultrasound in deionized water
Clock, drying.
In step 1:
Alkali wash water is mixed to get by ammonium hydroxide, hydrogen peroxide, water, volume ratio 1:1:5；
Pickling solution is mixed to get by hydrochloric acid, hydrogen peroxide, water, volume ratio 1:1:5.
Alkali cleaning and pickling, first is that carrying out cleaning removal to the dirt of silicon chip surface, two be exactly that silicon chip surface is allowed to carry hydroxyl-
OH, convenient for being linked together with methoxyl group one end of silane by polycondensation reaction.Ammonium hydroxide and hydrogen peroxide are all solution states, mutually
It does not react, can be dispersed in water, form uniform mixed liquor.
It is rinsed, and is cleaned by ultrasonic 2 minutes with a large amount of deionized waters after alkali cleaning and pickling；
The silicon wafer of surface hydroxylation is with being dried with nitrogen.
In step 2:
In the toluene solution of mercaptopropyi trimethoxy silane, the volumetric concentration 1-5% of mercaptopropyi trimethoxy silane；
The silicon wafer of silanization is respectively placed in toluene, the toluene/ethanol mixed liquor of ethyl alcohol volume ratio 1:1, ethyl alcohol, deionized water
In each ultrasonic 2 minutes.
In step 3:
Silicon wafer after immersion is rinsed with deionized water, ultrasound 2 minutes.
In step 4:
Silicon wafer after reaction is rinsed with deionized water, ultrasound 2 minutes.
In step 5:
In the mixed solution of silver nitrate and polyvinylpyrrolidone, the concentration of silver nitrate is 0.25mM, polyvinylpyrrolidine
The concentration of ketone is 0.75mM.
Method of the present invention first has to carry out silanization treatment to silicon wafer, but has selected and do not had in the prior art
The different silane related to, i.e. hydrosulphonyl silane, sulfydryl slough H in aqueous solution+After make positively charged (and the amino silane of silane
It is negatively charged in the solution), so as to be attracted each other by electrostatic by Ag+Ionic adsorption (and amino silane band in the solution
Negative electricity, absorption Ag cannot be achieved in it+The purpose of ion.In addition because the denominator of hydrosulphonyl silane, is also not excluded for other sulfydryls
Silane, as mercaptopropyi triethoxy or other silane for carrying sulfydryl also can achieve absorption Ag+The purpose of ion, thus
It is final to implement, complete this programme), the sodium borohydride being then added is by Ag+ Ion is reduced to Ag atom in situ, this Ag atom is made
For seed crystal, become the place of later period Ag nanocrystal nucleation, growth, for guarantee Ag nano particle uniformly, densification be distributed in silicon
On piece provides reliable guarantee.It is carried out by the circulation of growth step, the gap between Ag nano particle gradually reduces, and puts down
Equal gap can may detect 10 within 10nm-11The Raman spectrum of the R6G solution of mol/L, enhancement factor is up to 107Quantity
Grade, the Raman spectrum in this substrate at 9 positions of random test, 610 cm of R6G molecule-1The phase of spectral intensity at displacement
It is 4% to standard deviation.
Organic molecule with double-functional group --- mercaptopropyi trimethoxy silane plays the role of bi-directional chaining, it
One end links silicon chip surface, and the other end carries negative electrical charge, stretches to except silicon wafer, under the action of electrostatic force, can inhale silver ion
It invests on silicon wafer.The use of the linking agent of this special role, to ensure that Argent grain equably, is controllably distributed in silicon chip surface
Provide feasibility.The processing method (such as concentration, time, solvent) of this linking agent determines that it is dense in the distribution of silicon chip surface
Degree, thus the distribution density of Argent grain is influenced indirectly.Sodium borohydride is added to be restored, the silver being assembled on silicon wafer is available from
Seed crystal, silver-colored seed crystal provide place for the growth of later period silver nano-grain, and after adding reducing agent ascorbic acid, silver ion is in quilt
Seed crystal face is grown on while reduction.Silver nano-grain consistency and particle size can by absorption silver ion when
Between or the cycle-index of ascorbic acid reduction step increase.It therefore, can by the optimization of above mentioned every factor
To obtain the SERS substrate that silver nano-grain is uniformly distributed and arranges finer and close.
It the step of this programme step more than the prior art, i.e. generation Ag seed crystal, i.e., is carried out at silane to silicon wafer
After reason, does not place it into directly in the nanoparticle growth liquid of silver (or gold), but lead to first on the position of silane
Cross absorption Ag+Ion and reduction generate Ag seed crystal.This is a crucial step, and the generation of seed crystal is for Ag nano particle
Can be grown on silicon wafer play the role of it is conclusive.Seed crystal is the basis of later period silver nanoparticle grain growth, and seed crystal is as brilliant
Core opens the process that crystal grain is grown here (that is, on silicon wafer), just can be exactly in the induction of seed crystal and the effect of guidance
Fine and close and uniform Argent grain distribution is obtained on silicon wafer.Silicon wafer after silane treatment is placed directly within growth-promoting media (as special
The method taken in sharp CN201510753537.X and patent CN201510973724.9) in, this processing in fact can make
Argent grain grows that the probability on silicon wafer is not high, and the Argent grain largely generated is also in the solution.
Embodiment 1:
1) it cuts out and is first placed in 10ml alkali wash water (ammonium hydroxide: hydrogen peroxide: water=1:1:5, volume ratio) for the silicon wafer of 1cm × 1cm
It impregnates 15 minutes, is rinsed later with a large amount of deionized waters, and be cleaned by ultrasonic 2 minutes；
2) above-mentioned silicon wafer is placed in 10ml pickling solution (hydrochloric acid: hydrogen peroxide: water=1:1:5, volume ratio) again after and impregnates 15
Minute, it is rinsed later with a large amount of deionized waters, and be cleaned by ultrasonic 2 minutes, so that silicon chip surface hydroxylating；
3) after above-mentioned silicon wafer is dried with nitrogen, 10ml, the toluene of 40 DEG C of mercaptopropyi trimethoxy silane (MPTMS) are placed in
In solution (volumetric concentration 5%), kept for 4 hours, so that silicon wafer silanization；
4) above-mentioned silicon wafer is taken out, toluene, toluene/ethanol mixed liquor (volume ratio 1:1), ethyl alcohol, deionized water are respectively placed in
In each ultrasonic 2 minutes；
5) it walks on and is impregnated 6 hours in the silver nitrate solution for the 0.25mM that the silicon wafer handled is placed in 10ml.It takes out and uses later
Deionized water is rinsed, ultrasound 2 minutes；
6) silicon wafer handled is walked on, is placed in the sodium borohydride solution of the 5mM of 10ml, is reacted 30 minutes；It takes out later
It is rinsed with deionized water, ultrasound 2 minutes；
7) silicon wafer handled is walked on, the polyvinylpyrrolidone of the silver nitrate and 0.75mM that are placed in the 0.25mM of 10ml is mixed
It closes and is stirred 30 minutes in liquid, instill 1ml later, the ascorbic acid solution of 0.5mM reacts 30 minutes；
8) silicon wafer after taking out step reaction is rinsed with a large amount of deionized waters, and ultrasound 2 minutes in deionized water, drying
?.
Embodiment 2:
1) it cuts out and is first placed in 10ml alkali wash water (ammonium hydroxide: hydrogen peroxide: water=1:1:5, volume ratio) for the silicon wafer of 1cm × 1cm
It impregnates 15 minutes, is rinsed later with a large amount of deionized waters, and be cleaned by ultrasonic 2 minutes；
2) above-mentioned silicon wafer is placed in 10ml pickling solution (hydrochloric acid: hydrogen peroxide: water=1:1:5, volume ratio) again after and impregnates 15
Minute, it is rinsed later with a large amount of deionized waters, and be cleaned by ultrasonic 2 minutes, so that silicon chip surface hydroxylating；
3) after above-mentioned silicon wafer is dried with nitrogen, 10ml, the toluene solution of mercaptopropyi trimethoxy silane (MPTMS) are placed in
In (volumetric concentration 5%), kept for 24 hours, so that silicon wafer silanization；
4) above-mentioned silicon wafer is taken out, toluene, toluene/ethanol mixed liquor (volume ratio 1:1), ethyl alcohol, deionized water are respectively placed in
In each ultrasonic 2 minutes；
5) it walks on and is impregnated 24 hours in the silver nitrate solution for the 0.25mM that the silicon wafer handled is placed in 10ml.It takes out and uses later
Deionized water is rinsed, ultrasound 2 minutes；
6) silicon wafer handled is walked on, is placed in the sodium borohydride solution of the 5mM of 10ml, is reacted 30 minutes；It takes out later
It is rinsed with deionized water, ultrasound 2 minutes；
7) silicon wafer handled is walked on, the polyvinylpyrrolidone of the silver nitrate and 0.75mM that are placed in the 0.25mM of 10ml is mixed
It closes and is stirred 30 minutes in liquid, instill 1ml later, the ascorbic acid solution of 0.5mM reacts 30 minutes；
8) silicon wafer for taking out step 7, is rinsed well with deionized water, repetition step 7, and 3 times.It finally takes out reacted
Silicon wafer is rinsed with a large amount of deionized waters, and ultrasound 2 minutes in deionized water, drying.
Embodiment 3:
1) it cuts out and is first placed in 10ml alkali wash water (ammonium hydroxide: hydrogen peroxide: water=1:1:5, volume ratio) for the silicon wafer of 1cm × 1cm
It impregnates 15 minutes, is rinsed later with a large amount of deionized waters, and be cleaned by ultrasonic 2 minutes；
2) above-mentioned silicon wafer is placed in 10ml pickling solution (hydrochloric acid: hydrogen peroxide: water=1:1:5, volume ratio) again after and impregnates 15
Minute, it is rinsed later with a large amount of deionized waters, and be cleaned by ultrasonic 2 minutes, so that silicon chip surface hydroxylating；
3) after above-mentioned silicon wafer is dried with nitrogen, 10ml, the toluene solution of mercaptopropyi trimethoxy silane (MPTMS) are placed in
It in (volumetric concentration 1%), is stored at room temperature 30 hours, so that silicon wafer silanization；
4) above-mentioned silicon wafer is taken out, toluene, toluene/ethanol mixed liquor (volume ratio 1:1), ethyl alcohol, deionized water are respectively placed in
In each ultrasonic 2 minutes；
5) it walks on and is impregnated 24 hours in the silver nitrate solution for the 0.25mM that the silicon wafer handled is placed in 10ml.It takes out and uses later
Deionized water is rinsed, ultrasound 2 minutes；
6) silicon wafer handled is walked on, is placed in the sodium borohydride solution of the 5mM of 10ml, is reacted 30 minutes；It takes out later
It is rinsed with deionized water, ultrasound 2 minutes；
7) silicon wafer handled is walked on, the polyvinylpyrrolidone of the silver nitrate and 0.75mM that are placed in the 0.25mM of 10ml is mixed
It closes and is stirred 30 minutes in liquid, instill 1ml, the ascorbic acid solution of 0.5mM later；
8) silicon wafer for taking out step 7, is rinsed, later repeatedly step 7,3 times with deionized water.Finally take out reacted silicon
Piece is rinsed with a large amount of deionized waters, and ultrasound 2 minutes in deionized water, drying.
The substrate prepared by this method, is shown in Fig. 1, Argent grain on a silicon substrate densely, be evenly distributed, between particle
Average distance be less than 10nm, this substrate can detect 10-11R6G solution when mol/L concentration.And on this base not
With the measurement result (see figure 2) at position, closely, relative standard deviation (RSD) is 4%, illustrates the uniformity of substrate very
It is good.
The contents of the present invention are not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And to any equivalent transformation that technical solution of the present invention is taken, all are covered by the claims of the invention.
Claims (9)
1. the preparation method of silver nano-grain compacted zone on silicon wafer, it is characterised in that:
The following steps are included:
Silicon wafer: being first placed on alkali wash water by step 1 and pickling solution impregnates each 15 minutes, so that silicon chip surface hydroxylating；
Step 2: the silicon wafer that step 1 is obtained is placed in the toluene solution of mercaptopropyi trimethoxy silane, at a temperature of 40 DEG C
Reaction 4-10 hours, or react 24-40 hours at room temperature, so that silicon wafer silanization；The toluene of mercaptopropyi trimethoxy silane
In solution, the volumetric concentration 1-5% of mercaptopropyi trimethoxy silane；
Step 3: the silicon wafer that step 2 is obtained, which is placed in the silver nitrate solution of 0.25mM, to be impregnated 6-24 hours；
Step 4: the silicon wafer that step 3 obtains is taken out, is placed in the sodium borohydride solution of 5mM, is reacted 30 minutes；
Step 5: taking out the silicon wafer that step 4 obtains, be placed in the mixed solution of silver nitrate and polyvinylpyrrolidone, stirring 30
Minute, the ascorbic acid solution of 1ml, 0.5mM are instilled later；
Step 6: the silicon wafer that step 5 obtains is taken out, is rinsed with deionized water, is repeated step 5 2-5 times；
Step 7: finally taking out reacted silicon wafer and rinsed with a large amount of deionized waters, and ultrasound 2 minutes in deionized water, blows
It is dry.
2. the preparation method of silver nano-grain compacted zone on silicon wafer according to claim 1, it is characterised in that:
In step 1, alkali wash water is mixed to get by ammonium hydroxide, hydrogen peroxide, water, volume ratio 1:1:5.
3. the preparation method of silver nano-grain compacted zone on silicon wafer according to claim 1, it is characterised in that:
In step 1, pickling solution is mixed to get by hydrochloric acid, hydrogen peroxide, water, volume ratio 1:1:5.
4. the preparation method of silver nano-grain compacted zone on silicon wafer according to claim 1, it is characterised in that:
It in step 1, is rinsed, and is cleaned by ultrasonic 2 minutes with a large amount of deionized waters after alkali cleaning and pickling.
5. the preparation method of silver nano-grain compacted zone on silicon wafer according to claim 1, it is characterised in that:
In step 1, the silicon wafer of surface hydroxylation is with being dried with nitrogen.
6. the preparation method of silver nano-grain compacted zone on silicon wafer according to claim 1, it is characterised in that:
In step 2, the silicon wafer of silanization be respectively placed in toluene, ethyl alcohol volume ratio 1:1 toluene/ethanol mixed liquor, ethyl alcohol, go
Each ultrasonic 2 minutes in ionized water.
7. the preparation method of silver nano-grain compacted zone on silicon wafer according to claim 1, it is characterised in that:
In step 3, the silicon wafer after immersion is rinsed with deionized water, ultrasound 2 minutes.
8. the preparation method of silver nano-grain compacted zone on silicon wafer according to claim 1, it is characterised in that:
In step 4, the silicon wafer after reaction is rinsed with deionized water, ultrasound 2 minutes.
9. the preparation method of silver nano-grain compacted zone on silicon wafer according to claim 1, it is characterised in that:
In step 5, in the mixed solution of silver nitrate and polyvinylpyrrolidone, the concentration of silver nitrate is 0.25mM, polyethylene pyrrole
The concentration of pyrrolidone is 0.75mM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710707061.5A CN107460462B (en) | 2017-08-17 | 2017-08-17 | The preparation method of silver nano-grain compacted zone on silicon wafer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710707061.5A CN107460462B (en) | 2017-08-17 | 2017-08-17 | The preparation method of silver nano-grain compacted zone on silicon wafer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107460462A CN107460462A (en) | 2017-12-12 |
| CN107460462B true CN107460462B (en) | 2019-03-19 |
Family
ID=60549154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710707061.5A Active CN107460462B (en) | 2017-08-17 | 2017-08-17 | The preparation method of silver nano-grain compacted zone on silicon wafer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107460462B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108760713B (en) * | 2018-03-02 | 2020-11-17 | 西安工业大学 | Preparation method of uniform SERS substrate based on gold nanoparticles |
| CN110879221A (en) * | 2019-11-06 | 2020-03-13 | 广州供电局有限公司 | Silicon-based silver nano surface enhanced substrate and preparation method thereof |
| CN111793476B (en) * | 2020-07-09 | 2022-01-25 | 深圳先进电子材料国际创新研究院 | Heat conduction material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206357A (en) * | 2011-03-28 | 2011-10-05 | 复旦大学 | Surface-enhanced Raman scattering (SERS) tag microsphere and preparation method thereof |
| CN104162665A (en) * | 2014-08-29 | 2014-11-26 | 华东理工大学 | Gold-organic silicon-gold multilayer core-shell nano-structure and preparing method and application thereof |
| CN105386017A (en) * | 2015-11-09 | 2016-03-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing Raman-enhanced substrate with silicon surface modified by silver nanoparticles |
| CN105499602A (en) * | 2015-12-21 | 2016-04-20 | 上海交通大学 | Method for preparing SERS substrate compounded with gold nanoparticles based on reduction method |
| CN105823768A (en) * | 2016-04-25 | 2016-08-03 | 中国科学院高能物理研究所 | Detection chip based on surface enhanced raman scattering technique, preparation method and kit |
| CN106148925A (en) * | 2015-03-23 | 2016-11-23 | 中国科学院高能物理研究所 | A kind of preparation method of silver island material |
-
2017
- 2017-08-17 CN CN201710707061.5A patent/CN107460462B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206357A (en) * | 2011-03-28 | 2011-10-05 | 复旦大学 | Surface-enhanced Raman scattering (SERS) tag microsphere and preparation method thereof |
| CN104162665A (en) * | 2014-08-29 | 2014-11-26 | 华东理工大学 | Gold-organic silicon-gold multilayer core-shell nano-structure and preparing method and application thereof |
| CN106148925A (en) * | 2015-03-23 | 2016-11-23 | 中国科学院高能物理研究所 | A kind of preparation method of silver island material |
| CN105386017A (en) * | 2015-11-09 | 2016-03-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing Raman-enhanced substrate with silicon surface modified by silver nanoparticles |
| CN105499602A (en) * | 2015-12-21 | 2016-04-20 | 上海交通大学 | Method for preparing SERS substrate compounded with gold nanoparticles based on reduction method |
| CN105823768A (en) * | 2016-04-25 | 2016-08-03 | 中国科学院高能物理研究所 | Detection chip based on surface enhanced raman scattering technique, preparation method and kit |
Non-Patent Citations (1)
| Title |
|---|
| Large-Scale Uniform Two-Dimensional Hexagonal Arrays of Gold Nanoparticles Templated from Mesoporous Silica Film for Surface-Enhanced Raman Spectroscopy;Wang, Yi-Wen等;《The Journal of Physical Chemistry C》;20141010;第120卷(第42期);24382-24388 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107460462A (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107460462B (en) | The preparation method of silver nano-grain compacted zone on silicon wafer | |
| Yec et al. | Synthetic architecture of multiple core–shell and yolk–shell structures of (Cu2O@) n Cu2O (n= 1–4) with centricity and eccentricity | |
| Sun et al. | Investigating the multiple roles of polyvinylpyrrolidone for a general methodology of oxide encapsulation | |
| Chen et al. | Silver nanoparticles capped by oleylamine: formation, growth, and self-organization | |
| Deng et al. | Novel method to fabricate SiO2/Ag composite spheres and their catalytic, surface-enhanced Raman scattering properties | |
| Zhai et al. | Superparamagnetic plasmonic nanohybrids: shape-controlled synthesis, TEM-induced structure evolution, and efficient sunlight-driven inactivation of bacteria | |
| Liu et al. | Rapid fabrication of high quality self-assembled nanometer gold particles by spin coating method | |
| Liu et al. | Selective synthesis of hexagonal Ag nanoplates in a solution-phase chemical reduction process | |
| US20140077121A1 (en) | Generic Approach for Synthesizing Asymmetric Nanoparticles and Nanoassemblies | |
| CN108250745B (en) | A kind of strawberry-like poly-dopamine core golden shell nanocomposite and preparation method thereof | |
| Wang et al. | Facile synthesis of hollow urchin-like gold nanoparticles and their catalytic activity | |
| CN103286312A (en) | Surface-common-enhanced fluorescence surface-enhanced Raman multi-layer core-shell structure composite particles and preparation method of particles | |
| CN109530718B (en) | Preparation method of flower-shaped gold nanowire composite nanoparticles | |
| Hosseinifar et al. | Synthesis, characterization, and application of partially blocked amine-functionalized magnetic nanoparticles | |
| Imura et al. | Highly stable silica-coated gold nanoflowers supported on alumina | |
| Estrada-Mendoza et al. | Light absorption and scattering by silver/silver sulfide hybrid nanoparticles | |
| Lazzara et al. | Polymer templated synthesis of AgCN and Ag nanowires | |
| Watanabe et al. | Flow microreactor synthesis of gold nanoshells and patchy particles | |
| Wang et al. | Engineering structural diversity in gold nanocrystals by ligand-mediated interface control | |
| Oćwieja et al. | Gold nanoparticle layers on polystyrene microspheres of controlled structure and electrokinetic properties | |
| Kundu et al. | Photochemical synthesis of shape-selective palladium nanocubes in aqueous solution | |
| CN108152266B (en) | Core-shell material based on polydopamine, and preparation method and application thereof | |
| Luo et al. | Photochemical synthesis of crown-shaped platinum nanoparticles using aggregates of G4-NH 2 PAMAM dendrimer as templates | |
| Hanisch et al. | Synthesis of silver nanoparticle necklaces without explicit addition of reducing or templating agents | |
| CN110308136B (en) | Preparation method and application of noble metal and MoO3 self-assembly material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |